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HOA - CHE BIEN DAU KHI J KET QUA NGHIEN CLTU CHE TAO, O A N H GlA VA THU NGHIEM HE VI NHO TUONG ACID CHO XU LY VUNG CAN O A Y GIENG VIA CAT KET KS Nguyen Thi Ngpc Bich, ThS Trinh Thanh San, ThS Hoang Linh ThS Phan Vu Anh, ThS Hoang Thi Phuong, KS Lucfng Van Tuyen ThS Kieu Anh Trung, CN Cu Thj Viet Nga, KS Ngo Hong Anh Vien Dau Viet Nam Email: bichntn@vpi.pvn.vn Tom tat Bdi bdo gidi thieu mpt so kit qud ve nghiin cdu chi tgo he vi nhu tUang acid cho xd ly vung can ddy gieng; kich thudc hgt vd dp bin cua hi vi nhu Hi vi nhu cd tdc dp dn mon thdp htm dung dich acid d cimg nong dp Kit qua thit nghiim trin md hinh via cho thdy hi vi nhu tong hgp dUgc cd khd ndng phuc hoi dp thdm trin 90% ddi vdi mdu ldi tdng Miocene vd Oligocene md Bgch Ho Tdkhda: He vi nhu tuang acid, via cdt ket, dp thdm Gidi thieu Trong bai bao nay, nhdm tae gia gidi thieu kit qui tdi Uu hda t h i n h phan h i vi nhu tuang va dinh gia, thil Hiin nay, sin lugng dau cua nhieu gieng khai thic bj syt g i i m h i i n tupng nhiem ban vung can day gieng bdi sU hinh thinh, b i m dinh va tich tu eie can huu co va vo CO Trong giai doan 1988-2012, cd 776 l l n x y i y vung can day gieng tai md Bach Ho v l khai thic t h i m dupc 6,08 trieu tan dau Nhilu phuong phap xd ly vung c i n day gting da duac thCf nghiem va dng dyng rdng rai vdi mdc dp thinh edng khie Tren thye t l , XLf ly acid la phuong p h i p phd b i l n nhit nhim cai thiin dp tham eho vdng ein day gilng Tuy vac tinh trang ey the eua vdng can day gilng can xd ly, co the I p dung nhilu quy trinh va phan he acid phu hgp nhu: sd dung hon hop acid don thuin, nhu tUong acid, t i i n xy ly bang dung moi hydrocarbon (diesel), dau tho nong k i t hop vdi dung djch acid Myc t i i u cua phumig p h i p xd (y acid la hda tan cac tich tu vo co bit nhet hoac tao kinh d i n mdi gidp cii t h i i n hoac phyc hoi dp tham cho vdng c i n day gilng Tuy nhien, h i nhu tUcmg acid v i n tdn tai tfnh an mdn cac, hieu qua xOf ly khong kio dai, thdi gian tri ngin ban kinh xam nhap cda aeid khdng sau khiln tinh trang ngip nude eda via ngiy cing tang Qui trinh xd ly acid lap lai, hieu qua xd ly g i l m d i n nghiem he vi nhu tuong acid dng dung cho xd ly nhiem ban vung can day gieng via cat kit Thyc nghidm 2.1 Nguyin lieu va thiet bi 2.1.1 Nguyen lieu Cic hda chat de pha ehe nen he vi nhu tuong gom: dau diesel, xyfen, acid formic, K_EDTA, chat hoat ddng be mat khong ion ky hieu la HDBM 1, HDBM 2, butanol Day la kit qua eua q u i trinh khao sat lua chpn dua tren phan cda lang dong hdu ca (nhua, asphaltene, paraffin ranj v i lang dong vd co (CaCOj va CaSO^ ) Mau Idi duge thd nghiim dugc lay tu tang Miocene va Oligocene md Bach Ho Phong thf nghiem Md hinh hda va Vat iy via -Viin Nghien cdu Khoa hgc va Thiet ke Dau bien (NiPI) chuan bi 2.1.2.Thietbi 6ng chju nhiet (Ace Glass Incorporated Vineland NewJersey - USA); tu gia nhiet (MRC - Israel); may kfcti thudc hat (LA-950V2 HORIBA - Nhat Ban); may do nhdt (Fann Viscometer Model 35 SA-USA) Khacphychiin trang tren, nhom tac g i l thuoc Trung tam Nghiin cdu Tim kiem Thim dd va Khai t h i c Dau khf -Vien Dau khiViit Nam da nghien cdru c h i tao he vi nhu tucmg k i t hop nhdm hda pham xd ly ddng thdi can lang dpng hilu CO va vd ca Vdi kich thude nhd, eae hat vi nhu tuong ed t h i t h i m nhap siu vao vdng cd dp tham thap ma cac dung dich acid khae khong the xam nhap, giup tang pham vi xd ly va nang cao hiiu q u i cai thien dp tham vung can d i y gieng 2.2 Phuang phdp nghien cUu Xly dyng gian dd pha: Ba gian dd pha dUOe xay dung tuemg ufng vdi cic ty le khdi luong cua chat hoat dpng be mat (S) va chit ddng hoat ddng be mat (Co) la 1:1,2:1 va 3:1 theo phuang phap chuan dp PhUcffig phap quy hoach thue nghiim: Phan mem Modde 5.0 duac sd dung de xae dinh cac gia trj tdi uu 32 BAI Eri - s o 3r20A5 *i r PETROVIETNAM 2.3 Ddnh gid mdt sd chi tiiu didtliMig cda hi vinhu tUcmg Do kich thudc hat vi nhu bSng t h i l t bi LA-950V2 HORIBA (Nhat Bin) D6 ben pha va thdi gian taeh pha cCia he vi nhd d d i l u kiin via; Dp ben pha dugc t i l n h i n h theo phuong p h i p Bottle test [7, 8] CS dieu kiin nhiet dp eao, mau vi nhu tuong dugc dung trcng dng chju nhiet ehuyen dung c i n bd NIPI (Vietsovpetro) d i n h gia k h i n i n g phyc hdi dp tham t r i n t h i l t bj md hinh ddng chay 6a pha theo quy trinh cda Vietsovpetro [1] 2.4 h Quy trinh phan tich, ddnh gid kha ndng phuc hoi dp thdm cda mau loi sau xii ly bdng he vi nhu tUdng Thiet lap cdc md hinh via doi vdi mau loi via cdt kit va xdc djnh dp thdm ban ddu dat td gia n h i i t d nhiet dp vung can day g i l n g thdi gian gid Q u i trinh t i c h pha eua he vi nhu dupe quan sat sau moi khoing thdi gian xae djnh (30 phdt) + Gia cdng mau loi: Khoan mau tru (1 mau tang Miocene va mau tang Oligocene), say khd, b l o hda bang nudc via trudc thUc hiin thi nghiim; Do dp nhdt eua he vi nhd tuong tai nhiit dp phong bang t h i l t bj Fann Viscometer Model 35 SA Tde dp I n mdn cua he vi nhd duoc d i n h gia va so sinh vdi dung djch aeid formic eung ndng dd theo tieu chuan ASTM G31-72 va ASTM G1-03 [2,3] + Xae ^ n h dp tham khi, rdng; -1- Tac bac hda nudc d u S ^ ; + Do chilu d i i , dudng kinh m l u tru: mau tang Miocene va mau tang Oligocene ed ehieu dai lan luat la 4,79cm, 4,98cm va 7,14cm; dUdng kinh 4,94cm, 5,06cm 2.4 Thd nghiim khd ndng phuc hoi dd thdm trin md v i 5cm hinh vdt ly via tUcmg dng vdi dieu kien mdu Idi tdng Miocene vd Oligocene De d i n h g i l k h i ning xd ly can ling dong vung can day gieng via eat kit, nhdm t i e g i i d l phdi hgp vdi cic Chudn bj chdt luu Idm viec + Nudc biln; + Dau via dupe md phdng nhdt d dieu kien via eat kit: 70% d i u thd gieng 27 (MSP-1-BK-7) + 30% dau hda Do dp nhdt d i u d nhiit dp 110°C va 130°C; + D i u nhiem ban pha t h i m paraffin va asphaltene; + Nude ed khoang hda eao; + H i vi nhu tuong - k i t q u i cda phuong phap quy hoaeh thye nghiim khio sit tdi Uu hda d i l u kiin tao vi nhu tuong 2.4 ThCf nghiem ddnh gid phuc hoi dp thdm tren md hinh ddng chay da pha Chuan bi lap m l u loi vao bd giy mau, tang nhiit dd l i n ICC vdi mau Miocene v i 130°C vdi mau Oligocene, ap suat nen hdng P^|_ = 130atm; (tuong duong i p suat hieu dung P^^), ap suat lam viec P^,^ = lOOatm; bom bao hda d i u cho mau (5 lan the tich Id rdng) 5V^ theo chieu t h u i n Xie djnh dd tham dau ban dau cua mau md hinh via: K,; Bom dung djeh nude cd dp khoing hda cac vdi t h i tich 2V^ vdi AP - 20amt/m n h i m muc dfeh k i t tua can lang dpng vd co LOu gid mau tai d i l u kien via gid; Bam day d i u nhiem ban d l duoc ehuan bj vdi AP = 20 - 24amt/m, t h i tfch bom 2V^ t i t nhiit n g l m d nhiit dp Hinh I Thiftbl ddnh gid khd ndng phuc thdm cOa hi vi nhu titong trin md hinh dbng chay da phdng (nhim lang dpng paraffin va asphaltene), luu gid trcng - gid Sau dd nang nhiet dp l i n nhiit dp via Bom DAUKHl-sd3/2015 33 fl HOA - CHE BIEN D A U KHI dau md phdng dp nhdt theo ehilu thuan d AP = 20amt/m Xie dinh dp tham dau K^; 3.2 Kit qud khdo sdt dieu kien toi UU bdng phuangph6a quy hogch thUc nghiem Bom h i vi nhd tuang acid theo chilu ngugc vdi Thye hien thf nghiem theo phuong phap quy hoach ehilu tham vdi AP = 20amt/m, the tieh bOm 2V Bom thuc nghiim, tdi uu hda ham muc t i i u b i n g phuemg trinli day dau md phdng theo chilu thuan dAP = 50amt/m, the hdi quy bae Dya t r i n k i t q u i thye nghiem, ed t h i irtft tfch bom 3Vr Xae djnh dp tham dau K^ phuong trinh hdi quy mo ta sy phu thudc cda kfch thufic Tinh he sd phue hdi tham eua mau theo eong thdc: K^^-K,/[(K,+ KJ/2] hat vi nhu tuong (y) vao cac nhan td: tdc dd khuay (xl), ndng dd c h i t hoat ddng be mat {x2) va ndng dp aeid ^ nhu sau: y = 53.S Ket quii vd thio ludn \-9,80x,- 12.01xf +30,04X-, • 26.15 X -3.8 ix,x,-0.38x,x, 3.1 Xdy diing gidn pha Ba giin dd pha eua ba h i VNT-1, VNT-2, VNT-3 vdi tile S:Co tin l u o t i i 1:1,2:1 va 3:1 dupe t h i hiin d e l e Hinh - Vung tao h i vi nhu tUOng la vung gidl han bdi dudng cong b i n gian dd thinh phan Cac giin dd pha cda he vl nhd tuang (Hinh 2-4) eho thay cac phan eda h i VNT-3 (5:Co = 3:1) d l tao mpt vung vi nhd tuong mpt khoing rdng, md rgng ca v l phia pha dau va pha acid han he VNT-1 v l VNT-2 He VNT-3 duge lua chon cho eac nghiin edu sau vi cd dp b i n pha hon va cae thinh phan he vi nhu tUOng ed t h i thay ddi linh hoat hon i p dung cho tdng gilng khai thae eu the Bing Thdnh phan H | vi nhu tUoTng Dya vao so lieu thuc nghiim thu dupe, vdi sU hd tro cua phan mem Modde 5.0, nhom t i c g i l tim dieu kien khuay trdn tdi Uu, ndng aeid HCOOH va eac chat hda nhu de thu duoe he vi nhO tuong co kich thude hat phin bd nhd nhat He vl nhu tdi Uu cd kfch thude hat phan b6 nhd n h i t d^52,96nm Tien hanh tdi Uu hoa bang each v i b l mat 3D tM hiin eye trj cua h i tdi Uu (Hinh 5) Phuong trinh hdi quy p h i n i n h kha chi'nh xlc mo hinh thue nghiim, dieu khing dinh qua eae gia trj dp lich ehuan R'= 0,993 va tUong thich eda md hinh Q'= 0,943 vi nhu laong dux luo chon delihdo sdt T^ 16 khoi liftfng Chat hoat dong be mat SiCo ' HPBM1:HDBM2 ! DO:Xyiene HCOOH; K2EDTA;nU^ VNT-i" VNT-2 VNT-3 WinA Qan pha cua he VUI- 34 DAU KHl s o 3/2013 l(SCo=ll) ITinh Gian 36 cuo he VNT-2 (S:Co = 2-1} PETROVIETNAM 3.3 £>o kich thudc hgt thudc tap trung la 52,53nm, ehdng td phUOng phap quy K i t q u i sy phan bd kfch thudc hat theo eUdng dp eua m l u vi nhu tuong tdi Uu (ndng dd chat hda nhd 50%, ndng dd aeid formic 12%) dugc bieu dien b i n g dd thj p h i n bd kich thudc hat d Hinh hoach thye nghiim tren tUong ddi phu hgp vdi thyc t l Kit q u i eung hoan toan phu hop vdi b i n chat cua he vi nhu tuong da dUOc de cap d myc gidi t h i i u (kfch thude vi nhu tuang khoang 10 - 200nm) va d m l u phan Idn chi ehda mot loai hat (theo kich thudc) dam Kit q u i kich thudc hat cua h i vi nhu tUOng toi Uu (Hinh 6) cho thay mau vi nhu tuang ehda cac hat kich b i o sU phan tan ddng nhat va ben vdng, khd bj p h i vd eau true sau mpt thdi gian b l o q u i n dai Dua t r i n gian pha, d i l m Ml dugc chpn de t i l p tuc d i n h g i i mpt sd chi t i i u chit luong cda edng thu'c vi nhu tuong niy.Thanh phan h i vi nhu dUOe lUa chpn the hiin d Bing 3.4 Dp bin pha ddieu kien thudng Sau t h i n g thd nghiim d d i l u kiin nhiit dp phdng, VI nhu tuong acid v i n sudt, khdng he bj t i c h Idp va giQ nguyin m i u sic ban d i u (Hinh 8), ehdng td h i vi nhu thd nghiem b i n ve mat nhiet dong hpc Hinh Gidn cda he VNT-3 (S.Co=3:1) Bing Bdng ket qua dieu kien toi Uu duac lim ro bdng phuang phdp quy hoach thi/c nghiem J6cd6 Nong chlit hoa khu^y (vdng/phut) nhu (%) 49,51 202 Ndng acid (%) 12,07 Kich ' thiTdc hat (nm) ' 52,96 Ngoai quan Trong Kich thifcTc Hinh SubKn thiin kich thu&c hot« nhu nang chdt hoa nhd Surfactant vd Oddtimydoi v^t6cd6ldiudykbdng doi (tai diem tdi uu) Hinh Kel quo 3o phdn bo kich thudc hgt theo cuong dd cue he vi nhu Gian pha vi nhu tuong HDBM Ifinh He VI nhu toi uu tgi diem Ml tiin gidn so sdnh vung VI nhu tuan diabaheVNr-l(Sio=l:l),heVNT-2(S:Co=2:V.m-3(S-Co=i:l} DAU KHt - SO 3^)15 35 HOA - CHE BIEN D A U KHI Bong Thanh phan he vi nhu lUong MI Chat hoat d o n g be „,,s:Co = 3-l Ha , i nhu x o n g M l _ HDBM : H D B M = 2:1 HCOOH iKiEOTA: nif6c = 3:1:1 v„io„o _ c.i D0:Xylene-5.1 Chat hoat d o n g be mat = 50%, Dau = 30%, acid = % ~ HDBM (25%), HOBM (12,5%), n-Butanol (12,5%), DO (25%), xylen (5%), HCOOH (12%), K?EDTA (4%), nUdc (4%) 30 60 90 120 Thdi gian (phut) 150 Hinh9.HinhdnhhevinhQlimgMitrong4giddnhietd6cao HinhS Hinhdnh he vinhu tuong Ml ddieukiin nhietdgphong (trong, mdu vdng) Bdng Ket qud thd nhiet tmng gid cua hi vi nhu tumgMI Thdi gian (phut) 30 60 90 120 150 180 210 ' 240 Luang nudc tach (%) 0 10 15 20 20 20 he hoa phdm gid Bang Ket qud ddnh gia loc an mdn thip cua TT Hoa - ~ Formic % ! Nhiet t h i phim ngliiem - Hivinhu tuOng 3.S Thdi gian tdch pha ddiiu s (cm') llCC 27,90 IBO-C IIO-C 28,15 27,94 130°C 27,78 kiin nhiit dp cao cda hi vi Mau vi nhd tuong acid dugc dUng dng chju nhiet ehuyin dyng dat td gia n h i i t tai 130°C Quan sit su taeh pha cua vi nhu tUong sau 30 phut/Ian thdi gian gid Hinh va Bang la k i t qua t h d nhiet h i vi nhd tuong aeid d nhiet dp eao gid Mau vi nhu tuong acid van gid duoc mau sac on djnh va sudt sau 30 phut t h d nhiit Nhung sau gid t h d nhiet, m l u vi nhu tuong b i t dau bi van due va chuyin sang mau t r i n g sda, he vi nhu tuong bat dau bj p h i vd v i tieh pha Pha nude duge hinh t h i n h tCr t d b i n dudi d i y dng thd nhiit Trong quy trinh xd ly via bing vi nhu tuang thi sau gid vi nhu tUOng d l t h i m n h i p duoe vao vung ed dp tham thap (vdng can t i c ddng) v l du thdi gian tach acid de hda tan cin ling dgng vd co va lang dong hu'u co DMIKal-S03/2015 19,7491 19,2397 18,5235 1,2256 161,7258 19,1511 0,0886 11,7785 19,2348 19,119'? 0,1151 15,3910 19,4561 nhu tucmg Ml 36 ~T0931 ~ Toe an mon (mm/nam) 145,5431 m„ (g) j —j — Ket q u i t h i nghiem - mi(g) 18,3630 Am(g) _ (dung thOi dilm) Thdi gian gid d l d i m b l o eho h i vi nhu tuong dn dinh, khong bj tach Idp trUdc d i n dUdc vdng can t i e ddng Do do, k i t qua t h d nhiet cda he vi nhu tuong M l d Bang hoan toan phu hgp vdi t i i u ehuan cua Vietsovpetro ddi vdi nhd tUOng acid diing eho xdly g i l n g 3.6 Ddnh gid tdc dp dn mdn cda hi vinhu tUOng Ml Kit q u i tde dp an mdn thep cua he hda pham duoc trinh bay d Bang Kit qua Bang eho thay h i vi nhu tuang cd an mdn thep it hon rat nhieu so vdi acid formic rieng le (ndng dp 12%) va d i l u k i i n nhiet cang eao thi dd an mdn thep cda cic hda pham cing tang D i l u ehdng ^ h i vi nhu tUOng cd kha nang dc che an mon eao v l chinh sy hien d i i n eda pha dau h i vi nhu d l lam gilm tdc dp phan dng cua acid formic vdi t h i p PETROVIETNAM Bang Mot so thong sd vdi ly cuo mou loi via cat ket M a u loi Chieu dai DUijng cat k e t (cm) k i n h (cm) Tgng Miocene I Tang Miocene I Tang Oligocene BH-74.5-3-40 B BH-818.6-2-64 BH-16.10-3-95//2 , Do bao hoa ntrorc dU[%) 34 27 7,14 Thg tich rong (cm^j 19,2 18,4 Do rong '(%) ^ I i Do tham ; , khi(mD] _21,1 365" 18,73 " ' 306 28,5 Bing Luu lupng chdt thai qud trinh bam ep chai nhiem ban theo thM gian 6thi nghiem Qua t r i n h b d m ip c h ^ t n h i e m l>an y d ca LUu jUOng t h i i tieh luy (ml) : ' Luu lugng thai t h u c t e (ml) [ Thdj^gian (phut) LUu luong thai tich lOyJml) 5 ' 10 15 8,5 ! 1,5 Qua trinh biAn ep ep cch hat " 10 15 2,5 i 4,9 6,8 40 10,9 35 10,8 0,2 1^6 0,4 1 n h i i m b ^ n huTu ctf - - 45 18,6 0,4 50 "l8,8 0,2 Luu l u g n g t h i i thue t i (ml) Bing Luu lupng chat thdi qud Irinh bam ep chdt nhiem bdn theo thdi gian dthi nghiem Q u a t r i n h b t f m e p chat n h i e m b a n v o ccr Luu l u g n g thai t i c h luy (ml) 6,9 JLUu lUdng t h i i thUc te (ml) 3,2 i 9,8 , 12,6 2^9 _ 2^8 ' 18,2 ^J).8_ 55 18,9 0,1 ^ u a t r i n h bam e p chat n JTidi gian (phOt) LUu luang t h ^ i tich luy (ml) Luu lugng t h ^ i thifc tg (ml) LiAj li/dng xhki [hi/c t^ nhi^m ban v6 ca -TN (ml) "45 " 12,3 0,6 "so"^ 12,7 0,4 55 12,9 0,2 Liiu li/ang thar thi/c tg nhiSm bSn va co - TN3 (ml) Iilnh10.()dlhibiiudienluulugngduithdilhuctetrongqualrinhbamepchdtnhiembanlheothdigmillhinghiem2vd3 lU KHl-SO 3/2015 37 HOA - CHE BIEN DAU KHI 3.7 Thd nghiim khd ndng phuc hdi dp thdm trin md hinh vdt ly c h l I p suit d myc khong ddi d l theo doi va ghi laj via tuang iing v
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